WO2014119791A1 - Particules fines de cuivre revêtues d'un nouveau type et procédé de production associé - Google Patents

Particules fines de cuivre revêtues d'un nouveau type et procédé de production associé Download PDF

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WO2014119791A1
WO2014119791A1 PCT/JP2014/052514 JP2014052514W WO2014119791A1 WO 2014119791 A1 WO2014119791 A1 WO 2014119791A1 JP 2014052514 W JP2014052514 W JP 2014052514W WO 2014119791 A1 WO2014119791 A1 WO 2014119791A1
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copper
fine particles
copper fine
fatty acid
coated copper
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PCT/JP2014/052514
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English (en)
Japanese (ja)
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正人 栗原
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国立大学法人山形大学
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • H01B1/026—Alloys based on copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B22F1/102—Metallic powder coated with organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles

Definitions

  • the present invention relates to coated copper fine particles obtained by reducing fatty acid copper with a reducing compound and a method for producing the same. More specifically, the present invention relates to a method for producing copper fine particles using a reducing agent and fatty acid copper in an alkylamine.
  • a copper precursor compound such as acetylacetonato copper is mixed with an amine-based compound such as oleylamine to prepare a uniform mixture, and then a reducing agent is optionally added, followed by heating to obtain a copper ion species.
  • a method for producing cubic-shaped copper nanoparticles obtained by reducing a metal to a metal oxide state or a metal oxide state (Patent Document 1).
  • 6.5 to 8.5 times the amount of the copper precursor, oleylamine and dodecyl are used in order to make the form of the copper nanoparticles to be formed into a cubic form having a desired size.
  • An amine or the like needs to be used, and a large amount of organic solvent is also required for recovering the obtained copper nanoparticles.
  • a method for producing metallic copper fine particles whose surface is capped with a fatty acid including a step of heating and reacting (Patent Document 2).
  • the reaction solution needs to be heated to 200 ° C. (Example 1), while copper acetate is added with formic acid in the presence of oleic acid and oleylamine.
  • heating is performed at 130 ° C. (Example 2), and it is considered difficult to control the formation reaction of the copper fine particles by this method.
  • the present inventors have so far prepared a process of producing a composite compound by mixing a compound containing copper and a reducing compound, and copper fine particles coated with alkylamine by heating the composite compound in an alkylamine.
  • a process for producing coated copper fine particles without being limited by the supply of substances involved in the reaction see Patent Document 3.
  • a complex compound with a reducing compound is formed in advance, for example, a complex compound such as a complex of copper oxalate and hydrazine.
  • spontaneous decomposition can occur at a relatively low temperature in the coexistence state with the alkylamine, and coated copper fine particles coated with a protective film containing the alkylamine can be produced.
  • coated copper fine particles Although it is possible to produce coated copper fine particles, it is desirable to develop a process for producing coated copper fine particles that can be carried out at a lower temperature and with a simpler and more flexible synthesis process. Then, this invention makes it a subject to provide the manufacturing process of the covering copper fine particle which can be implemented at low temperature.
  • the inventors of the present invention perform the step of producing coated copper fine particles at a lower temperature by using a predetermined fatty acid copper as the copper compound. It became possible to improve the flexibility of the whole process. It has also been found that this process can easily and in large quantities produce fine copper particles that are stable in air, stable in particle size distribution, and stable.
  • the method for producing coated copper fine particles of the present invention includes a step of heating a mixture containing fatty acid copper, a reducing compound, and an alkylamine, and using fatty acid copper having 9 or less carbon atoms as the fatty acid copper.
  • the fatty acid copper may be dissolved or suspended in the presence of an alkylamine, mixed with a reducing compound, heated, or mixed with the fatty acid copper and the reducing compound in advance. It may be added and heated.
  • the production of the fatty acid copper and the mixing of the reducing compound are simultaneously performed by mixing the copper hydroxide, the fatty acid and the reducing compound in an appropriate solvent. Can be done automatically.
  • the solvent used in the method of the present invention is preferably a polar organic solvent such as 1-propanol or 2-propanol.
  • the method of the present invention by using a fatty acid copper having 9 or less carbon atoms as a starting material for producing copper fine particles, in addition to a process for obtaining an intermediate in which a molecule having a reducing action is previously bound to a starting material, even when the starting material is introduced into a mixture of alkylamine, which is a reaction medium and also a coating of copper fine particles, and a molecule having a reducing action, the coated copper fine particles can be produced satisfactorily. Moreover, it becomes possible to produce coated copper fine particles by a reaction at a lower temperature. As a result, according to the method of the present invention, the manufactured coated copper fine particles can be sintered at a lower temperature, and the degree of freedom of the process can be increased.
  • FIG. 2 is a powder X-ray diffraction (XRD) pattern of the coated copper fine particle powder synthesized in Example 1.
  • FIG. 2 It is the transmission electron microscope image and electron beam diffraction in the different magnification of the covering copper fine particle synthesize
  • FIG. 2 is a high-resolution electron microscope image of coated copper fine particles synthesized in Example 1.
  • FIG. 3 is a result of simultaneous thermogravimetric differential thermal analysis of coated copper fine particles synthesized in Example 1.
  • 3 is a powder X-ray diffraction (XRD) pattern of coated copper fine particles synthesized in Example 2.
  • XRD powder X-ray diffraction
  • FIG. 3 is an FE-STEM image of coated copper fine particles synthesized in Example 2.
  • FIG. 3 is an FE-STEM image of coated copper fine particles synthesized in Example 3.
  • FIG. 4 is a powder X-ray diffraction (XRD) pattern of coated copper fine particles synthesized in Example 4.
  • XRD powder X-ray diffraction
  • the reaction conditions such as the starting material, temperature, solvent and the like are adjusted without providing a separate step of forming a complex of such a copper-containing compound and a reducing compound.
  • the fatty acid copper and the reducing compound are mixed in advance in a solvent, preferably dissolved in the solvent, and these complexes are generated more rapidly. It is thought that it is easy to mix more uniformly. That is, in general, the reducing agent is often used in an aqueous medium, and the reduction reaction does not proceed uniformly because it is not uniformly mixed in an organic solvent-based reaction.
  • the reducing agent is often used in an aqueous medium, and the reduction reaction does not proceed uniformly because it is not uniformly mixed in an organic solvent-based reaction.
  • the solvent used in the method of the present invention is preferably a polar solvent in order to promote dissolution of fatty acid copper and the reducing compound.
  • generating a covering copper fine particle can be advanced efficiently at low temperature rather than before. For this reason, it is expected that the sintering temperature of the coated copper fine particles to be produced is further lowered than before.
  • the method for producing coated copper fine particles according to the present invention will be specifically described.
  • fatty acid copper As a raw material of copper used for producing the coated copper fine particles in the present invention, fatty acid copper having 9 or less carbon atoms can be used.
  • the term “fatty acid copper” is a salt compound of a fatty acid having 2 or more carbon atoms and copper, and the fatty acid may be either saturated or unsaturated.
  • select the fatty acid copper to be used because the properties such as solvent dispersibility and sinterability of the coated copper fine particles are affected by the difference in the carbon number of the fatty acid copper used. It is preferable to do.
  • fatty acid copper typically used one selected from the group consisting of copper acetate, copper propionate, copper butyrate, copper valerate, copper caproate, copper enanthate, copper caprylate and copper nonanoate or Two or more types of fatty acid copper.
  • these fatty acid coppers as the raw material for the coated copper fine particles, the degree of freedom of the process for producing the coated copper fine particles is improved, and the coated copper fine particles can be produced at a lower temperature. As a result, it is expected to lower the sintering temperature of the thin film produced using the coated copper fine particles of the present invention.
  • a reducing compound having a reducing action is mixed with the fatty acid copper mainly in an appropriate solvent.
  • a complex compound such as a complex is formed between the two compounds.
  • the reducing compound becomes an electron donor for copper ions in fatty acid copper and tends to cause reduction of copper ions. Therefore, by spontaneous pyrolysis compared to fatty acid copper used. It is thought that copper atoms are likely to be liberated.
  • the reaction is caused to occur within the complex produced in advance, thereby limiting the supply of substances involved in the reaction.
  • the copper atoms are supplied by causing a spontaneous decomposition reaction of a complex or the like by setting conditions such as temperature and pressure, and uniform coated copper fine particles can be produced.
  • the reducing compound used in this case include hydrazine compounds such as hydrazine, hydrazine hydrochloride, hydrazine sulfate, and hydrazine hydrate, sodium borohydride, and sodium sulfite.
  • Examples include sodium bisulfite, sodium thiosulfate, and sodium hypophosphite, but those having an amino group such as hydrazine and hydrazine compounds are preferred.
  • the reducing agent having an amino group easily forms a coordinate bond with a copper atom in the fatty acid copper, and easily forms a complex with the fatty acid copper while maintaining the structure of the fatty acid copper. This is because a reduction reaction of copper ions occurs.
  • any compound capable of forming a complex or the like that causes reduction / release of a copper atom in a temperature range that does not cause evaporation or decomposition of an alkylamine used as a reaction medium in a subsequent heating step may be used. It is not limited.
  • a high temperature is required for the decomposition, which causes evaporation and decomposition of the alkylamine itself as a reaction medium. For the reason, it becomes difficult to solve the problems of the present invention.
  • a compound selected from the group consisting of hydrazine, hydroxylamine, and derivatives thereof is particularly preferable. It is done. These compounds can form a complex by binding a nitrogen atom constituting a skeleton to a copper atom in a copper-containing compound through a coordination bond.
  • the reducing power is generally stronger than that of alkylamines, the resulting complex undergoes spontaneous decomposition under relatively mild conditions to reduce and release copper atoms, thereby reducing copper fine particles coated with alkylamine. Can be generated.
  • the hydrazine derivative is obtained by substituting one to three hydrogen atoms contained in hydrazine with a predetermined alkyl group, for example, methyl hydrazine, ethyl hydrazine, n-propyl hydrazine, i-propyl hydrazine, n- Butyl hydrazine, i-butyl hydrazine, sec-butyl hydrazine, t-butyl hydrazine, n-pentyl hydrazine, i-pentyl hydrazine, neo-pentyl hydrazine, t-pentyl hydrazine, n-hexyl hydrazine, i-hexyl hydrazine, n- Heptylhydrazine, n-octylhydrazine, n-nonylhydrazine, n-decyl
  • a hydroxylamine derivative is one obtained by substituting one of hydrogens contained in hydroxylamine with a substituent such as a predetermined alkyl group, hydroxyalkyl group, sulfoalkyl group or carboxyalkyl group.
  • a substituent such as a predetermined alkyl group, hydroxyalkyl group, sulfoalkyl group or carboxyalkyl group.
  • N, N-di (sulfoethyl) hydroxylamine, monomethylhydroxylamine, dimethylhydroxylamine, monoethylhydroxylamine, diethylhydroxylamine, N, N-di (carboxyethyl) hydroxylamine are preferred. It is possible to adjust the reactivity with fatty acid copper by using its derivatives instead of hydrazine and hydroxylamine as appropriate, and spontaneous decomposition under appropriate conditions according to the fatty acid copper used.
  • the resulting complex can be produced.
  • it is effective to promote the formation of a composite compound by using an appropriately selected hydrazine derivative.
  • the fatty acid copper and the reducing compound are preferably mixed by cooling to about 10 ° C. or less, more preferably about 5 ° C. or less, and most preferably about 0 ° C. or less.
  • the ratio of the reducing compound mixed with the fatty acid copper for the formation of the complex is equal to the molar ratio (hereinafter referred to as “constant ratio”) of both in the complex formed from the fatty acid copper and the reducing compound, or the like. It is preferable that the ratio is more enriched with reducing compounds. If the ratio of the reducing compound is equal to or less than the constant ratio in the complex or the like, fatty acid copper that does not form a complex or the like is generated, resulting in a metal atom that is not liberated, resulting in a decrease in the yield of copper fine particles.
  • the preferable mixing ratio of the reducing compound is 4 times or less of the ratio in the complex or the like.
  • a good complex or the like can be formed by mixing the reducing compound with fatty acid copper so as to be 1 to 2 times.
  • the reducing compound to be used can be used by mixing two or more kinds of reducing compounds depending on the properties thereof.
  • a reducing compound containing an appropriate additive component for the purpose of assisting the formation of a complex or the like within a range that does not inhibit the properties of the complex or the like to be generated.
  • a fatty acid copper and a reducing compound are mixed, the formation of a complex or the like is promoted by causing a polar solvent capable of dissolving them without causing a reaction with a substance in the system and as a reaction medium.
  • a uniform complex etc. can be produced
  • the polar solvent is preferably one having solubility in water (H 2 O) at room temperature.
  • Alcohols exhibiting solubility in water have a certain polarity, and the use of such alcohols can promote the formation of complexes such as fatty acid copper and a reducing compound. Although the specific action of such an alcohol is not clear, it is considered that complex formation is promoted by promoting contact with a water-soluble reducing compound while dissolving solid state fatty acid copper.
  • Examples of the alcohol showing the solubility in water include linear alkyl alcohols having one OH group, from methanol having 1 carbon atom to octanol having 8 carbon atoms.
  • the number of carbon atoms is 9 or more, it does not substantially dissolve in water, and even if such an alcohol is interposed during the formation of a complex or the like, the formation promoting action of the complex or the like is not observed.
  • phenols or those obtained by substituting hydrogen atoms of appropriate hydrocarbons having an ether bond in the molecule with OH groups can be used.
  • glycols containing two OH groups, glycerin containing three OH groups, Pentaerythritol and the like containing 4 OH groups are preferably used.
  • alcohol compounds examples include methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, allyl alcohol, benzyl alcohol, pinacol, propylene glycol, menthol, catechol, hydroquinone, salicyl alcohol, pentaerythritol, sucrose, Examples thereof include glucose, xylitol, methoxyethanol, triethylene glycol monomethyl ether, pentaerythritol, and the like, and polyethylene glycols including ethylene glycol, triethylene glycol, tetraethylene glycol, and pentaethylene glycol.
  • dimethyl (hydroxymethyl) phosphonate, dimethyl (2-hydroxyethyl) phosphonate, or the like can be used as the alcohol compound containing a phosphorus atom.
  • alcohol compounds such as 2- (trimethylsilyl) ethanol, 2- (trimethylsilyl) -1-propanol and triethylsilanol containing silicon atoms can be used.
  • the polar solvent used in a preferred embodiment of the present invention is an alcohol that exhibits extremely high solubility in water, and examples thereof include 1-propanol and 2-propanol. More preferred is 1-propanol.
  • the mixture of fatty acid copper and reducing compound produced above is mixed with a sufficient amount of alkylamine and heated to spontaneously decompose fatty acid copper.
  • Copper fine particles are obtained by the formation and aggregation of copper atoms by the reaction.
  • the coating by the alkylamine used on the surface of the copper fine particle arises in that case, the stable coated copper fine particle which is hard to be oxidized with oxygen in the air can be obtained.
  • the decomposition temperature of the fatty acid copper is desirably about 150 ° C. or lower.
  • the evaporation rate is high when an alkylamine having a high vapor pressure such as butylamine or hexylamine is used as the reaction medium. Therefore, the alkylamine used as a reaction medium is actually limited to a long chain having 8 or more carbon atoms, and the low-temperature sinterability of the coated copper fine particles is hindered.
  • the decomposition temperature of the complex is less than 130 ° C, more preferably 120 ° C, 110 ° C, or 100 ° C.
  • an alkylamine having about 6 carbon atoms can be used stably, and copper particles are generated under relatively mild conditions. It is possible to produce coated copper fine particles that are fine and have a narrow particle size distribution.
  • a low molecular weight alkylamine having a relatively low boiling point can be used, so that the protective coating can be easily removed and coated copper fine particles that can be sintered at a low temperature can be easily produced.
  • Fatty acid copper to be used is different from the reaction to produce a copper atom by a reducing compound, but for example, when nonanoic acid copper is used as the fatty acid copper and hydrazine (or a derivative thereof) is used as the reducing compound, By mixing copper nonanoate and hydrazine and the like, a complex composed of both compounds is produced. By mixing and heating this with alkylamine, copper nonanoate undergoes thermal decomposition even at a low temperature of about 100 ° C. Manufactured.
  • nonanoic acid and alkylamine existing in the system prevent invasion of oxygen existing outside the system, adhere to the reduced copper atoms, and finally coat the copper fine particles, Even when thermal decomposition is performed in the atmosphere, it is considered that oxidation of copper atoms is suppressed and stable coated copper fine particles are produced.
  • various fatty acids having different carbon numbers are used, or by adjusting the molecular weight of the alkylamine, the particle size of the generated copper fine particles is desired from several nm to about 100 nm. It is possible to adjust the size.
  • the first step of mixing the above-described fatty acid copper and the reducing compound, and the second step of heating the complex in the presence of an alkylamine to produce copper fine particles include 1 It can be carried out simultaneously or sequentially in one container. “Simultaneously” means that copper fine particles are produced by mixing fatty acid copper, a reducing compound, and an alkylamine at the same time, and preferably adding a polar solvent thereto to solubilize, followed by heating at about 100 ° C. Can do.
  • the first step and the second step can be performed sequentially, and the heating temperature at this time may be the same or different. More preferably, the first step is performed by cooling to about 10 ° C. or less, and the second step is performed by heating to about 150 ° C., more preferably about 100 ° C.
  • Alkylamine When a mixture of fatty acid copper and a reducing compound is heated, the alkylamine mixed with the mixture mainly functions as a reaction medium for the decomposition reaction of the complex as described above, and is generated by the reducing action of hydrazine. It is considered that protons are trapped and the reaction solution is inclined to be acidic and copper atoms generated by oxygen in the air are prevented from being oxidized.
  • the alkylamine used in the present invention can be appropriately selected from known alkylamines according to the thermal decomposition conditions of the complex used, the properties expected of the copper fine particles to be produced, and the like. .
  • the alkylamine used in the thermal decomposition of the complex may constitute a coating of copper fine particles together with the fatty acid.
  • the thermal decomposition conditions of the complex to be produced and the coated copper fine particles to be produced are expected.
  • it can be appropriately selected from known alkylamines.
  • the alkylamine used in the thermal decomposition of the mixture is appropriately selected according to the purpose of the coated copper fine particles to be produced as described above.
  • Examples of the alkylamine (monoamine) having one amino group in the molecule include 2-ethoxyethylamine, dipropylamine, dibutylamine, hexylamine, cyclohexylamine, heptylamine, 3-butoxypropylamine, octylamine, nonylamine Alkylamines such as decylamine, 3-aminopropyltriethoxysilane, dodecylamine, hexadecylamine, octadecylamine, and oleylamine are practical in terms of industrial production and availability.
  • hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine and dodecylamine having 6 to 12 carbon atoms are more preferably used. These may be used alone or in combination of two or more.
  • examples of the alkyldiamine having two amino groups in the molecule include ethylenediamine, N, N-dimethylethylenediamine, N, N′-dimethylethylenediamine, N, N-diethylethylenediamine, N, N′-diethylethylenediamine, 1 , 3-propanediamine, 2,2-dimethyl-1,3-propanediamine, N, N-dimethyl-1,3-diaminopropane, N, N′-dimethyl-1,3-diaminopropane, N, N— Diethyl-1,3-diaminopropane, 1,4-diaminobutane, 1,5-diamino-2-methylpentane, 1,6-diaminohexane, N, N′-dimethyl-1,6-diaminohexane, 1, Examples thereof include, but are not limited to, 7-diaminoheptane and 1,8-d
  • the alkylamine used for the thermal decomposition of the complex one kind of alkylamine may be used, or a plurality of alkylamines may be mixed and used.
  • the alkylamine used as the reaction medium is preferably a liquid at room temperature because it is easy to handle. Therefore, when using an alkylamine that has a large molecular weight and is solid at room temperature, it is mixed with a small molecular weight. It is preferable to use it in a liquid state.
  • the coated copper fine particles according to the present invention typically have an average particle size of 50 nm or less, and further an average particle size of 20 nm or less. Therefore, when the protective film provided on the surface is detached, It is possible to form a copper film by sintering even at an extremely low temperature as compared with the copper powder.
  • a fatty acid contained in fatty acid copper used as a source of copper atoms and an alkylamine used in the thermal decomposition of the complex form a protective film that can be easily detached by using a high vapor pressure. Sintering at a lower temperature is possible.
  • the coated copper fine particles produced are prevented from being oxidized by forming a strong protective film, and can be stored for a long time even in the air.
  • At least a part of the protective film covering the surface of the copper fine particles of the present invention contains the above-mentioned fatty acid copper and / or alkylamine, but the content of the coated copper fine particles relative to the weight, that is, the coverage is 15 wt. % Or less is preferable.
  • the fatty acid and alkylamine forming the protective film are eliminated and the copper fine particles are brought into direct contact with each other, thereby forming a conductor, and at a temperature of about 200 ° C. or less.
  • copper atoms constituting the copper fine particles are diffused and fused with each other, and the conductorization progresses. This phenomenon is because the fatty acids and alkylamines that form the protective film are weakly bonded to the surface of the copper fine particles due to the coordinate bond via the carboxyl group or amino group, and these can be removed relatively easily. It is thought to be because.
  • the ink dispersed in an organic solvent is printed in a desired shape by various methods such as inkjet printing, and heated to a predetermined temperature in an inert atmosphere to remove the protective film, Since the exposed copper fine powders cause sintering, copper wiring and the like can be easily formed by printing. It is also possible to perform the sintering after coating the coated copper fine particles in the form of a paste or powder.
  • the coated copper fine particles according to the present invention are used to form a conductor layer on the non-conductive surface instead of the conventional electroless plating or the like, and the metal layer is pressed between the metals. Therefore, it can be used for an adhesive layer for mechanically and electrically joining metals together.
  • the material and shape of the substrate to which the ink or paste containing the coated copper fine particles is applied are not particularly limited.
  • the material and shape of the substrate to which the ink or paste containing the coated copper fine particles is applied are not particularly limited.
  • thermoplastic resin, thermosetting resin, glass, paper, metal, silicon, ceramics, etc. can be used.
  • thermoplastic resin examples include polyethylene, polyethylene terephthalate, polypropylene, polyvinyl chloride, polystyrene, acrylonitrile-butadiene-styrene copolymer resin, acrylonitrile-styrene copolymer resin, polycarbonate, polyacetal, polybutylene terephthalate, polyphenylene oxide, polyamide, Polyphenylene sulfide, polysulfone, polyethersulfone, polyether-etherketone, polyarylate, aromatic polyester, aromatic polyamide, fluororesin, polyvinylidene chloride, polyvinyl alcohol, polyvinyl acetate, polyvinyl formal, polyvinyl butyral, polymethyl methacrylate And cellulose acetate.
  • thermosetting resin examples include phenol resin, urea resin, xylene resin, urea resin, melamine resin, epoxy resin, silicon resin, diallyl phthalate resin, furan resin, aniline resin, acetone-formaldehyde resin, alkyd resin, and the like.
  • the ceramic means inorganic compounds such as oxides, carbides, nitrides, borides and the like. For example, alumina (Al 2 O 3 ), silicon nitride (SiN), silicon carbide (SiC), aluminum nitride (AlN) ), Zirconium boride (ZrB 2 ), and the like.
  • the step of forming a predetermined film or the like on the substrate using ink containing coated copper fine particles is not particularly limited as long as it is a method capable of forming a film with a desired thickness, and general spin coating, spray coating, etc. Can be used.
  • the process of forming a pattern serving as a wiring precursor on a substrate with a film containing coated copper fine particles can use various conventional printing methods such as a screen printing method, an ink jet printing method, and an intaglio. Printing, letterpress printing, lithographic printing, and the like can be used.
  • the use of the metal film obtained by making a film containing coated copper fine particles into a conductor is not limited to electrical wiring, and can be used for mirror surfaces for optical devices, various decorations, and the like.
  • the thickness of the film formed on the substrate with the ink containing the coated copper fine particles can be appropriately set according to the purpose of the metal film obtained by making the conductor. If it is a normal electric wiring etc., a favorable characteristic can be acquired by forming a film
  • Example 1.2 The copper fine particles obtained in Example 1.2 were dispersed in toluene, and this was dropped onto a transmission electron microscope (TEM) substrate (carbon support film) to attach the copper fine particles to the TEM substrate. From the field emission transmission electron microscopic image (FE-TEM image) (JEOL JEM-2100F), it was found that spherical copper fine particles having a particle diameter of 10 nm or less were observed and large particles of 100 to 200 nm were also included. (Fig. 2) High-resolution TEM (HR-TEM) observation was performed on nano-particles of 10 nm or less, which are considered to be susceptible to air oxidation, and the lattice spacing of the observed lattice image is 0.21 nm. This coincided with the lattice spacing of the (111) plane of copper (FIG. 3), so no component derived from copper oxide was observed from the electron microscope.
  • HR-TEM High-resolution TEM
  • thermogravimetric differential thermal analysis In order to examine the content of protective molecules in the copper fine particle powder obtained in Example 1.2, simultaneous thermogravimetric differential thermal analysis (TG-DTA) was performed (FIG. 4).
  • TA instrument SDTQ600 was used, and the temperature was raised at 10 ° C. per minute under a pure nitrogen stream (150 mL per minute). By heating from room temperature to 250 ° C., a two-stage weight reduction was observed. When the temperature exceeds 400 to 500 ° C., the weight reduction becomes constant, and 5.3% by weight of the weight reduction rate at this time is the weight of the organic protective molecule covering the surface of the copper fine particles. From this weight loss, the copper based yield in Example 1.2 was calculated to be 96%.
  • thermogravimetric mass spectrometry Mass spectrometry (TG-Mass) of the desorbed protected molecules was performed using a mass analyzer JEOL (JMS-Q1050GC) while following the thermogravimetric decrease of the copper fine particle powder obtained in Example 1.2. .
  • the ionization method was carried out with EI and PI (photoionization) under a heating condition of 15 ° C. per minute under a helium stream (100 mL per minute). It was found that both the component derived from fatty acids (acetic acid and nonanoic acid) and the protective molecule derived from hexylamine were eliminated by the thermogravimetric decrease in the first stage up to 200 ° C. A component derived from nonanoic acid was detected in the thermogravimetric decrease in the second stage at 200 ° C. or higher.
  • Example 1.2 The copper fine particles obtained in Example 1.2 were dispersed in toluene to prepare a 50% by weight copper fine particle ink. This ink was dropped on a glass substrate and applied using a bar coater (Eiwa Hagi Seisakusho ⁇ 8 ⁇ 300 mm) to prepare a copper-gloss nanoparticle thin film. The obtained copper luster nanoparticle thin film was placed in an electric furnace (KDF S-70), the protective molecules were removed by heat and the particles were sintered together (sintering conditions: under argon, the heating rate was 10 ° C./min. 1 hour at each temperature reached (200, 220, 240, 260 ° C)). As shown in FIG.
  • Example 5 the copper fine particle thin film obtained in Example 1.2 was made into a conductor by heating at 200 ° C., and heated to 260 ° C. to have a volume resistivity (5.0 ⁇ cm, copper bulk resistance (1.7 ⁇ cm)). About 3 times the volume resistance).
  • the volume resistivity is calculated from the surface resistance measured with a four-end needle surface resistance measuring instrument (Kyowa Riken, K-705RS) and the film thickness obtained from a field emission scanning electron microscope (FE-SEM, JEOL JSM-7600F) image. did.
  • Example 2 Synthesis of copper fine particles using copper hydroxide (II) as a starting material
  • Example 2.1 ⁇ Electron microscope observation> The copper fine particles obtained in Example 2.1 were dispersed in toluene, and this was dropped on the TEM substrate, thereby attaching the copper fine particles to the TEM substrate. From the FE-STEM image (JEOL JSM-7600F), copper fine particles having two particle size distributions were observed. The particle size distributions were 7.6 ⁇ 2.3 nm (FIG. 7 (a)) and 24 ⁇ 3.3 nm (FIG. 7 (b)), respectively. In addition to the spherical shape, it was found that there were many prisms and hexagonal plates.
  • thermogravimetric differential thermal analysis In order to examine the content of protective molecules in the copper fine particle powder obtained in Example 2.1, a thermogravimetric differential thermal analysis (TG-DTA) was performed. By heating from room temperature to 250 ° C., a two-stage weight reduction was observed. When the temperature exceeds 400 to 500 ° C., the weight reduction becomes constant, and 9.2% by weight of the weight reduction rate at this time is the weight of the organic protective molecule covering the surface of the copper fine particles. From this weight loss, the copper based yield in Example 2.1 was calculated to be 81%.
  • TG-DTA thermogravimetric differential thermal analysis
  • Example 3 Method in which the order of addition of hexylamine and hydrazine was changed in the method of Example 2.
  • 0.62 g (6.3 mmol) of copper (II) hydroxide, 2.0 g (13 mmol) of nonanoic acid, 1-propanol 0.9 mL was added, and it heated and stirred at 100 degreeC using the aluminum block type heating stirrer.
  • 2.57 g (25.4 mmol) of hexylamine was added and stirred for 6 minutes.
  • This solution was ice-cooled, and 0.628 mL (12.7 mmol) of hydrazine monohydrate dissolved in 1 mL of 1-propanol was added.
  • thermogravimetric differential thermal analysis In order to examine the content of protective molecules contained in the copper fine particle powder obtained above, a thermogravimetric differential thermal analysis (TG-DTA) was performed. By heating from room temperature to 250 ° C., a two-stage weight reduction was observed. When the temperature exceeds 400 to 500 ° C., the weight reduction becomes constant, and 6.4% by weight of the weight reduction rate at this time is the weight of the organic protective molecule covering the surface of the copper fine particles. From this weight loss, the yield based on copper in Example 5 was calculated to be 92%.
  • TG-DTA thermogravimetric differential thermal analysis
  • Example 4 Synthesis of Copper Fine Particles Using One Type of Fatty Acid Copper fine particles were synthesized in the same manner as in Example 2 by replacing nonanoic acid with other fatty acids (3 to 7 carbon atoms).
  • Example 5 Synthesis of copper fine particles using two types of fatty acids In the same manner as in Example 2, two types of fatty acids (1: 1 in molar ratio) were simultaneously added to synthesize copper fine particles.

Abstract

La présente invention aborde la question de fourniture d'un procédé de production de particules fines de cuivre revêtues susceptible d'être mis en œuvre à de basses températures. L'invention concerne un procédé de production de particules fines de cuivre revêtues, caractérisé par l'inclusion d'une étape de chauffage dans laquelle un mélange contenant un acide gras de cuivre en C9 ou inférieur, un composé réducteur, et une alkylamine est chauffé.
PCT/JP2014/052514 2013-02-04 2014-02-04 Particules fines de cuivre revêtues d'un nouveau type et procédé de production associé WO2014119791A1 (fr)

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